Process for the manufacture of synthetic resins with urethane groups, which also contain carboxyl groups and can be diluted with water

ABSTRACT

The present invention relates to a process for the manufacture of thermosetting synthetic resins with urethane groups, which contain carboxyl groups and masked isocyanate groups and can be diluted with water, and which are manufactured by reaction of a compound (a) which contains alcoholic hydroxyl groups and carboxyl groups, with a masked isocyanate (b) in inert organic solvents. The present invention also relates to the use of the synthetic resins manufactured according to the invention as binders in coating agents for electrophoretic lacquering. The following advantages are achieved by the process of the present invention: Binders which can be diluted with water and are suitable for the electrophoretic coating process are obtained, which are distinguished by very good throwing power and by very good resistance of the stoved films to washing lyes or aqueous sodium chloride solution at 0* to 100*C.

United States Patent Broecker et al.

[4 1 July 29, 1975 PROCESS FOR THE MANUFACTURE OF SYNTHETIC RESINS WITH URETHANE GROUPS, WHICH ALSO CONTAIN CARBOXYL GROUPS AND CAN BE DILUTED WITH WATER Inventors: Bernhard Broecker, Hamburg;

Wolfram Plettner, Glinde, both of Germany Reichold-Albert-Chemie Aktiengesellschaft, Hamburg, Germ any Filed: Dec. 12, 1973 Appl. No.: 424,111

Assignee:

Foreign Application Priority Data Dec. 14, 1972 Switzerland 018260/72 US. Cl. 260/18 TN; 117/161 KP; 204/181; 260/29.2 TN; 260/775 CR; 260/775 TB Int. Cl.'- C08G 22/16; C08G 22/32; C08G 51/24 Field of Search 260/775 TB. 18 TN.29.2 TN. 260/775 CR References Cited UNITED STATES PATENTS 8/1957 Seeger et al. 260/775 TB 3/1959 Seligman 260/775 TB 1/1967 Sueling et a1. 260/775 TB 3,438,922 4/1969 Ueno ct al. 260/775 TB 3.660.359 4/1972 Labana 260/775 TB 3,719,522 3/1973 Johnson ct al. 260/775 TB 3,773,729 11/1973 Wakimoto ct a1. 260/775 TB 3.799.854 3/1974 Jerabek 260/29.2 TN

Primary ExaminerH. S. Cockeram Attorney, Agent, or FirmGordon W. Hueschen [57] ABSTRACT The present invention also relates to the use of the synthetic resins manufactured according to the invention as binders in coating agents for electrophoretic lacquering. The following advantages are achieved by the process of the present invention:

Binders which can be diluted with water and are suitable for the electrophoretic coating process are obtained, which are distinguished by very good throwing power and by very good resistance of the stoved films to washing lyes or aqueous sodium chloride solution at 0 to 100C.

8 Claims, No Drawings PROCESS FOR THE MANUFACTURE OF SYNTHETIC RESINS WITH URETHANE GROUPS, WHICH ALSO CONTAIN CARBOXYL GROUPS AND CAN BE'DILUTED WITH WATER BACKGROUND OF THE INVENTION or aminoplasts. The corrosion resistance achieved with these binders is inadequate.

Methoden der organischen Chemie (Methods of Organic Chemistry) (Houben-.Weyl), volume XIV/2, Georg Thieme Verlag, Stuttgart, describes, on pages 61 to 65, that isocyanates can be masked by reacting them with compounds which are split off again at elevated temperature. On page 64 it isstated that it is also possible to manufacture so-called mono-adducts which are obtained by reaction of polyisocyanates with masking components in such ratios that one isocyanate group remains free.

It is furthermore stated there that the presence of tertiary amine accelerates the reverse decomposition of the masked isocyanate groups. If such masked isocyanates are mixed with compounds carrying alcoholic hydroxyl groups and carrying carboxyl groups, turbid mixtures are as a rule obtained and additionally turbid films are produced after stoving. It was therefore completely surprising that the synthetic resins manufactured according to the invention give clear films on stoving. Furthermore, it was completely surprising thatthe aqueous solutions manufactured by neutralisation with ammonia or organic amines display excellent stability even when tertiary amines are employed as neutralising agents.

German Offenlegungsschrift 1,794,045 describes a process for the manufacture of a storage-stable polyurethane with masked isocyanate groups, wherein a polyisocyanate is reacted partly with phenol and partly with aliphatic compounds capable of reactions with isocyanates. However, this product is only storage-stable in an excess of phenol and is unsuitable for the manufacture of binders which can be diluted with water.

German Auslegeschrift 1,061,013 describes a process for the manufacture of lacquers wherein masked isocyanates are reacted with compounds with active hydrogen atoms. However, these masked isocyanates are incompatible with the component (a) according to the invention and are therefore unsuitable for the reaction.

German Offenlegungsschrift 2,020,905 describes a process for the manufacture of high molecular blocked isocyanate polymers in which partially blocked isocyanates having at least one free NCO group are reacted with compounds containing active hydrogen. ,Polyester-polyols, polyether-polyols or copolymers containing OH are used as such high moleculancompounds. However, the products thus obtained are eithe rnot compatible with water or, if they are compati'ble'with water, are neither suitable for electrophoretic application, since they are of non-ionic structure, no ripos'sess, in the form of stoved films, sufficient resistance to water or aqueous sodium chloride solution, as is shown by comparison test 3..

German Offenlegungsschrift 2,118,692 or U.S. Pat. No. 3,773,729 describes a process for the manufacture of blocked isocyanate polymers which are obtained by reaction of a polyisocyanate having at least one free isocyanate group and at least one blocked isocyanate group with a compound containing OHand carrying carboxyl groups. However, the process described there has the disadvantage that undesired side-reactions frequently occur during the reaction and that gelling fre quently takes place (comparison test 6). Furthermore. this process frequently gives products which when dissolved in organic water-miscible solvents display thixotropic behaviour.

2.'Field of the invention The present invention also relates to the use of the synthetic resins manufactured according to the invention as binders in coating agents for electrophoretic lacquering. The following advantages are achieved by the process of the present invention:

1. Binders which can be diluted with water and are suitable for the electrophoretic coating process are obtained, which are distinguished by very good throwing power and by very good resistance of the stoved films SUMMARY The present invention relates to a process for'the manufacture of thermosetting synthetic resins with urethane groups, which contain carboxyl groups and masked isocyanate groups and can be diluted with water, and which are manufactured by reaction of a compound (a) which contains alcoholic hydroxyl groups and carboxyl groups. with a masked isocyanate (b) in inert organic solvents. characterised in that as the compound (a) there are used copolymers, individually or as mixtures, which contain alcoholic hydroxyl groups and carboxyl groups, have a molecular weight of about 300 to about 10,000, a hydroxyl equivalent weight of 200 to 900 and acid numbers of about 30 to 150, based on carboxyl groups, and which must be soluble in inert polar organic solvents, only those copolymers being employed of which the carboxyl groups are not capable of significant reaction with masked isocyanate groups at temperatures of to C over the course of about one hour, and as the masked isocyanate (b) there is used a polyurethane which contains at least one masked isocyanate group and which has been obtained by reaction of a polyisocyanate with a free isocyanate group and at least one masked isocyanate group and at most up to 5 masked isocyanate groups with a compound carrying low molecular alcoholic hydroxyl groups, having a molecular weight of about l202,000 and a hydroxyl equivalent weight of about 60-500, the compound having been chosen from the group consisting of esters of fatty acids with polyols, wherein the polyols should be at least trifunctional but preferably should contain more than 3 hydroxyl groups but at most 6 hydroxyl groups, and diols which carry terminal yalkyl acrylates or mcthacrylates; andpolyoxypropyl- OH groups and in which 3-8 carbon atoms are aliphatiene acrylates'ormethacrylates of the general formula:

cally bonded between the OH groups. and that the l H C=(C CH CH CH I OCH- .CH .-OCH2-CH O-CH-;CHOH (l) components (aH-(b) are reacted at temperatures of80 wherein n represents values between 2 and 6, R is byto 150C, that the component (a) is employed in such m drogen or a methyl group and the compound of the foramounts that the end product has acid numbers bemula (l) or mixtures of these compounds having hytween about 30 to 120, that the proportion of calcudroxyl numbers of about I00 to 200. lated isocyanate groups (introduced when manufactur- In place of the hydroxyalkylacrylate it is also possiing the component b) is between 7.5 and 20 by ble to use allyl'compounds, such as allyl alcohol, alweight (relative to the weight of the end product) and lyloxy propanol, trimethylpropane diallyl ether, pentathat the end product is completely soluble in a 50 7! erythritol triallyl ether and similar compounds. strength solution in ethylene glycol monobutyl ether The vinyl ester of an a-alkylalkanemonocarboxylic and has a viscosity between 150 and 700 cP in this soluacid. which has become'known by the name of Versatic tion at 25C and that the amount of the component (b) Acid, is also outstandingly suitable for use as a plasticiswhich is employed is such that the mixture of compo- 20 ing'monomer. The a-alkylalkanemonocarboxylic acids nent (a)+(b) before reaction contains 2 to l5 7! by are based on a C C and C -acid which results from weight of masked isocyanate groups relative to the sum the pioneering work of Dr. H. Koch of the Max-Planckof (a)+(h). lnstitut fur Kohlenforschung in Muhlheim, Federal Republic of Germany. According to this work, the a-al- As the component (a) containing alcoholic hydroxyl kylalkanoic acids are mainly a mixture of C C and groups and carboxyl groups and having a molecular c -monocarboxylic acids. The acids are completely weight of about 300 to l0.000 and a hydroxyl equivasaturated and are very heavily substituted at the carbon lent weight of about 200 to 900 and acid numbers of atom in the a-position. Acids with two hydrogen atoms about to 150 it is possible to use: Copolymers of on the a-carbon atom are not present and only 6-7 4-20 acrylic acid and/or methacrylic acid, -70 "/1 ofthese acids contain a hydrogen atom on the a-carbon of plasticisingcopolymerised monomers, such as alkyl fltomn ad on. y c material is Present (DeuISChe acrylates or alkyl methacrylates in which the alkyl radi- Farben Zeitschrift, issue 10/16" year Of P CaI On. cal contains 4 to l2 carbon atoms, it being possible for page 435 the copolymer optionally also to contain 5-35 7( of Suitable polymer resins are mentioned in Table 1. other monomers. such as styrene. vinyltoluene, acrylo- 35 Those polymer resins mentioned in Table 2 are parnitrile and 8-15 7: of hydroxyalkyl acrylate being conticularly preferred within the scope of the present intained in the acrylate or methacrylate copolymer. exve'ntion and give light-coloured binders with very good amples of usable hydroxyalkyl acrylates being: Hydroxresistance to wash lyes.

Table l Copolymer Monomer carrying Monomer carrying OH Further monomers. Viscosity in cP at 25C carboxyl groups. groups. in ii by weight in 7: by weight (measured at strength in in 7: by weight ethylene glycol monobutyl ether) 14 hydroxyethyl 5t) vinylversatate A 15 acrylic acid methacrylate 21 methylmeth- 470 acrylate l5 hydroxycthyl 5U vinylversatate B 20 acrylic acid methacrylate l5 methylmeth- 545 acrylate l6 hydroxypropyl 49 vinylversatate C 20 acrylic acid acrylate l5 methylmeth- 480 acrylate lo hydroxybutyl 49 vinylvcrsatate D 20 acrylic acid acrylate l5 mcthylmeth- 440 acrylate 47 Z-ethylhexyl- E 20 acrylic acid ally] oxypropanol acrylate 400 20 styrene Table 2 Copolymer Monomer carrying Monomer carrying OH Further monomers, viscosity in c? at 25C.

carboxyl groups. in groups. in 7( by weight in 7: by weight (measured at 50% strength in by weight ethylene glycol monobutyl ether) 20 hydroxyethyl 40 l-ethylhexyl A 20 acrylic acid methacrylate acrylate. 4l0

, 20 styrene g g 4(l2 ethylhexyl B 20 acrylic acid 15 allyloxypropanol acrylate 490 25 styrene it) acrylic acid 25 hydroxyethyl 40 Z-ethylhexyl V C 10 methacrylic acid methacrylate acrylate 550 15 styrene Table 2 Continued Copolymer Monomer carrying Monomcrcarrying OH Further monomers.

viscosity in cP at 25C.

carboxyl groups, in /1 groups. in 7: by weight in /z by weight (measured at 50% strength in by weight ethylene glycol monobutyl ether) D 20 acrylic acid 2O hydroxyethyl 2O vinylversatate 370 acrylate 2O mcthyl'methacrylate 2O acrylic acid 20 hydroxyethyl 40 isobutyl acrylate 470 methacrylate 20 styrene l hydroxyethyl 4O Z-ethylhexyl F 20 acrylic acid methacrylate acrylatc 500 25 acrylonitrile l5 hydroxyethyl 45 Z-ethylhexyl G acrylic acid methacrylate acrylate 436 25 styrene l5 hydroxyethyl 40 I-ethylhexyl H acrylic acid methacrylatc acrylate 432 styrene Especially suitable copolymers to be employed in step (a) have molecular weights of about 300 to about 10,000, a hydroxyl equivalent weight of 200 to 900 and acid numbers of about to 150 of carboxyl groups groups, such as l,4-butanediol or l,6-hexanediol, are also suitable.

Suitable hydroxyl group containing compounds are given in Table 3.

Table 3 fatty acid polyol molar ratio number of free or oil hydroxyl groups isomeric mixture of pentaerythritol l l 3 isononanic acid pentaerythritol 1.5 l 2.5 trimethylol propane l l 2 glycerol l l 2 coconut oil pentaerythritol l 2 8 coconut oil trimethylol propane l 2 6 dehydrated Caster oil trimethylol propane l l 2 fatty acid tall oil fatty acid trimethylol propane l t l I! linseed oil fatty acid pentacrythritol l l 3 dehydrated caster oil pentaerythritol l L7 6.7

and are soluble in inert polar organic solvents. These copolymers contain so many carboxyl groups that the resins have acid numbers of between 80 and 150, the chosen unsaturated acids having as high an acidity as possible, that is a pK valueof 4. The other monomers should not easily be saponified, that is 2 ethylhexyl acrylate is more suitable than butylacrylate and vinylversatate is suited best. Styrene also is more suitable than methylmethacrylate. In all cases, however, a compromise has to be found for all polymerization parameters. The viscosity of the resins should amount to between 320 and 640 c? at 25C, measured at 50 strength ethylene glycol monobutyl ether.

Possible components (b) are polyurethanes with at least one blocked isocyanate group, which are obtained by reaction of a polyisocyanate group with molecular weights of 100 to 1,000, having at least one free and one masked isocyanate group, with a low molecular compound carrying alcoholic hydroxyl groups, having a molecular weight of about 120 to 2,000 and a hydroxyl equivalent weight of 60 to 500.

Suitable compounds, carrying hydroxyl groups, of this type are above all esters of fatty acids with polyols, wherein the polyols should be at least trifunctional but should preferably contain more than 3 hydroxyl groups and at most 6 hydroxyl groups. Suitable polyols of this type are trimethylolpropane, glycerine, pentaerythritol, hexanetriol, sorbitol and sucrose. Suitable fatty acids are unsaturated fatty acids, such as linseed oil fatty acid, soya oil fatty acid, tall oil fatty acid, linoleic acid, elaidic acid, castor oil fatty acid andiricinoleic acid and/or saturated fatty acids, such as coconut oil fatty acid, pelargonic acid and isononanoic acid. Diol s with terminal OH groups, wherein 3-8 aliphatically bonded carbon atoms should be present between the OH As polyisocyanates with at least one blocked isocyanate group it is possible to use compounds which are obtained by reacting arylene-diisocyanates or their'alkylation products, such as phenylene-diisocyanates, naphthylene-diisocyanates, diphenylmethanediisocyanates, toluylene-diisocyanates, dior tri-isopropylbenzenediisocyanate or triphenylmethanetriisocyanate, aralkyldii'socyanates, such at (isocyanatophenyl)-ethylisocyanate or dixylylenediisocyanates, ethylene glycol diphenyl ether-2,2- diisocyanate, diethylene glycol diphenyl ether-2,2- diisocyanate, naphthalene-l ,4-diisocyanate, l, l dinaphthyl-2,2-diisocyanate, bisphenyl-2,4'- diisocyanate, diphenyl-4,4-diisocyanate, benzophenone-3,3' -diisocyanate. l-methylbenzene-2,4,'6- triisocyanate, naphthalene-l ,3,7-triisocyanate, diphenylmethane-2,4,4-triisocyanate, triphenylmethane- 4,4,4"-triisocyanate, 3-methoxyhexane-diisocyanate, octane-diisocyanate, Q,Q-diisocyanate-l ,4- diethylbenzene, cyclohexane-l,3-diisocyanate. lisopropylbenzene-2,4-diisocyanate, l-chlorobenzene- 2,4-diisocyanate, diphenyl ether-2,4' diisocyanate, diphenyl ether-4,4'-diisocyanate and polyphenyl isocyanate of the general formula NCO NCO

NCO

n01. amides. imides or lactams of carboxylic acids. such as. for example. e-caprolactam. succinimide. phthalimide. maleimide and acrylic acid amide. and also malonic acid esters. such as malonic acid diethyl ester.

malonic acid dimethyl ester. and aeetoacetic acid esters, such as acetoacetic acid methyl ester and acetoacetic acid ethyl ester.

Amongst the polyisocyanates there are particularly preferred technical mixtures of 65-80 7: by weight of 2,4-toluylenediisocyanate and 35-20 by weight of 2.6-toluylene-diisocyanate or hexamethylenediisocyanate alone.

Amongst the'masking components there are particularly preferred: Phenol and e-caprolactam.

The reaction for manufacturing the component (b) is carried out by mixing and warming. the reaction being continued until no further free isocyanate is detectable (by titration with dibutylamine, for instance). On average. reaction times of 3 to 10 hours are required. The reaction is in general carried out in the presence of anhydrous inert solvents. for example in the presence of dioxane. methyl ethyl ketone. methyl isobutyl ketone. ethyl acetate, butyl acetate, acetone, benzene, xylene and toluene. The reaction temperature should be at least C below the reverse decomposition temperature of the thermally crosslinkable isocyanate groups. It lies. depending on the masking component. between 20 and 120C and preferably between 60 and 80C.

The ratio of masked polyisocyanate and lowmolecular compounds carrying alcoholic hydroxyl groups is so chosen that in the reaction the resulting polyurethane only retains a few hydroxyl groups. if any. that is to say the molar ratio of OH groups'to free isocyanate groups is in the reaction between 15:1 and 1:1.

The component (b) thus obtained is then reacted with .the component (a) by mixing and warming. The reaction temperature is determined by the reverse decomposition temperature of the masked isocyanate groups, that is to say it is chosen to be sufficiently high that at least apart of the blocked isocyanate groups react with a part of the hydroxyl groups of the component (a). The fact that this takes place can be ascertained from the increase in the viscosity of the reaction mixture.

The reaction between the components (a)+(b) is preferably carried out in the presence of inert solvents. such as acetone. methyl ethyl ketone. methyl isobutyl ketone. ethyl acetate. xylene and the like. The solvent chosen naturally depends on the reaction temperature. The reaction is continued until the desired final viscosity is reached. The viscosities of the end products should be between 150 cP and 700 cP at C. measured at 50 7! strength in butylglycol. Under the chosen conditions. the carboxyl groups of the component (a) do not as a rule participate in the reaction. If after a reaction time of 1 hour a decrease in the acid number of more than 5 units takes place in the reaction, either the reaction temperature has been chosen to be too high or the component (a) of the mixture is unsuitable for the reaction because of its carboxyl group being too strongly acid.

After completion of the reaction between the components (a) and ,(b) the inert solvents are removed by distillation. optionally under reduced pressure. At this stage. if the components (a) and the components (b) have been chosen correctly qualitatively. there must not only be 2-15 /1 by weight of thermally crosslinkable isocyanate in the end product, but the end product must also have an acid number of between and 1.00 and the solid resin must dissolve clearly in ethylene glycol monobutyl ether at 20C in at least a weight ratio of 1:1.

The end products are then diluted with hydrophilic solvents. Suitable hydrophilic solvents of this nature are above all monoethers of ethylene glycol. such as ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether and ethylene glycol monobutyl ether. However. lower alcohols. such as propanol. isopropanol and butanol. ketone-alcohols. such as diacetone-alcohol. and lower ketones. such as. for example. methyl ethyl ketone. are also suitable. The resins are then neutralised with ammonia or organic amines and can thereafter be diluted in any desired proportions with water. By organic amines there are to be understood. in this context, compounds which give a pH value of at least 8 in 10% strength aqueous solution at 20C. As such it is possble to use. for example, triethylamine, triethanolamine. triisopropanolamine. diglycolamine, diethylamine. piperidine, pyridine. morpholine. diethanolamine, dimethylethanolamine and methylethanolamine, but anorganic bases. such as potassium hydroxide and sodium hydroxide. are also suitable. The new synthetic resins, capable of dilution with water. obtained according to the process of the invention can be used as sole binders in aqueous coating agents. They are particularly suitable for electrophoretic lacquering. When used as electrophoresis binders. the new synthetic resins produced according to the invention are above all distinguished in that even products of relatively low molecular weight. the viscosity of which lies in the range of 64 to 226 cP, measured at 50 7r.strength in butyl glycol at 25C. show excellent values of the throwing power. above all after neutralisation with ammonia. This makes it possible to dilute the resins with only relatively small amounts of hydrophilic solvents so that the aqueous solutions then only contain extremely small amounts of. organic solvents. Furthermore. the electrophoretic baths are distinguished by excellent stability.

The new synthetic resins producedaccording to the invention can be used as sole binders for aqueous stoving lacquers. The stoving temperature of coatings made thereof varies between and C depending on the masking component used. The coating films obtained after stoving are distinguished by particularly good corrosion resistance. They can therefore be used as a primer. In addition to being used as priming resins, the new products made according to the invention can also be used as single-coat binders. The one-layer coatings thus obtained are distinguished by good adhesion. good elasticity and good stability of the colour shade. Particularly when using polyisocyanates based on aliphatic isocyanates, the binders according to the invention are also distinguished by excellent stability to weathering. i

The coatings made from these products are furthermore distinguished by excellent stability to wash lyes; the products are above all very resistant to boiling dilute detergent solutions.

350 g of toluyl'ene-diisocyanate are dissolved in 400 g of methyl ethyl ketone. 0.2g of dibutyl-tin dilaurate is added and 188g of phenol are then added. After the exothermic reaction has subsided.- the reaction mixture is kept at 60C until the isocyanate contenthas fallen to 2.1 mvaI/g. The product may probably be described by the following formula: t

A s ll ==N NH-'- (lb-O I This solutionwas then addeddr'opwiseat 80C to 195 g of an ester which was obtaine'd by esterification of 158 g of isononanoic acid with 135 g ofpentaerythritol at 220C, and the reaction batch was kept at 80C until the content of free NCO groups was practically zero. The content of masked isocyanate is 13.2 by weight (relative to solid resin).

MANUFACTURE OF TllEPRE-PRODUCT u The instructionsgiven for pre-prod'uct I are. followed.

Then, however, the instructions given below are followed: I

This solution was thenadded dropwise at 80C to 375 g of an ester which was obtained by trans-esterification of 300 g of Castor oil with 75 g of pentaerythritol in the presence of 0.2 g of calcium acetate and thereaction mixture was kept at 80C until the content of free NCO groups was practically'zero.

The content of masked isocyanate is 9.2 by weight (relative to solid resin). I

MANUFACTURE OF THE PRE-PRODUCT III 940 g of phenol-masked toluylene-diisocyanate (see pre-product I) are slowly added to90 g of 1,4-butylene glycol at 60C. The mixture is kept at 80C until the isocyanate content of free isocyanate has fallen to zero.

The content ,of masked isocyanate is. 15.5 by weight (relative to solidresin).

MANUFACTURE OF'THE .PRE-PRODUCT iv The procedure followed is as in the manufacture of the pre-product I'but instead of the phenol 226 g of e-caprolactam are employed. The mixture is kept until an isocyanate content of 1.95, mval/g is reached and is then reacted with the isononanoic .acid ester as described in the manufacture of the pre-product I. The content of masked isocyanate is 12.5 70 by weight (relative to solid resin).

MANUFACTURE oF PRE-PRODUCT v MANUFACTURE OF'PRE-PRODUCT V1 350 g'of commercial mixture of isomers of 2,4-and 2,6-toluylene-diisocyanate are dissolved in 200 g of methyl ethyl ketone. 0.2g of dibutyl tin dilaurate are added and also a total of 170 g e-caprolactam in small portions. After ceasing of the exothermic reaction the mix is kept at C until the content of isocyanate has dropped to 3.5 mval/g. The solution is then added dropwise at C to 345 g of the ester obtained by esterification of. 158 g of commercial mixture of isomers of iso'nonamic acid and 135' g of trimethylolpropane. The vmix is kept at 80C until the content of isocyanate has dropped to zero. I

The content of-masked isocyanate amounts to 7.3 by weight (relative to solid resin).

' MANUFACTURE OF PRE-PRODUCT VII The procedure followed is as in the manufacture of the pre-product VI. Then the solution of the masked isocyanate, however, is added'dropwise at 70C to 410 g of the ester obtainedby csterification of 270 g of coconut oil and g of trimethylolpropane at 250C. The mix is kept at 70C until the content of free isocyanate has dropped to zero. The content of masked isocyanate amounts to 6.7 72 by weight (relative to solid resin).

MANUFACTURE OF PRE-PRODUCT VIII The procedure followed is as in the manufacture of the pre-product VI. Then however, the solutionof the masked isocyanate is added dropwise at 70C to 360 g of the ester obtained by transesterification of 270 g of coconut oil with 90 g of pentaerythritol. The mix is kept at 80C until the content of free isocyanate has dropped to Zero.

The content of masked isocyanate amounts to 7 71 by weight (relative to solid resin).

MANUFACTURE OF THECOMPONENT a 200 g of acrylic acid, 200 g of hydroxyethyl methacrylate, 200 g of styrene and 400 g 2ethylhexyl acrylate are mixed with 30 g of Iaurylmercaptan and dissolved in 400 g of methyl isobutyl ketone. 30 g of ditert.-butyl peroxide are added thereto at l30l40C. The mixture is heated under reflux until the solids content has reached 70 EXAMPLE 1 700 g of the.resin solution obtained above (component a,) are mixed with 710 g of pre-product I and heated to C until.. th e viscosity, measured at 50% strength in methyl isobutyl ketone at 25C, has reached 436 cP. The solvent is then removed by vacuum distillation and the resin is diluted with ethylene glycol monobutyl ether to a solids content of 74 70. After neutralisation with ammonia, the product can be diluted with water in all proportions The resin is suitable for use as an electrophoretic single-coat resin and after stoving for 30 minutes at 170C gives lacquer films of outstanding resistance to wash Iyes (Test 1).

-MANUFA CTURE OF THE COMPONENT a 400 of 2-ethylhexyl acrylate, 150 g of allyloxyp ropa nol, 100 g.,0f acrylic acid, 350 g of styrene, 20 g of laurylrnercaptan and 30 g of di-tert.-butyl peroxide are mixed. 250 g of the mixture are heated to C.

After 40 minutes, the remaining 3/4 are added dropwise and the reaction mixture is kept at 130C until the solids content has reached 96 7t (1 hour at 1 10C).

The unreacted monomers are then removed by vacuum distillation and 200 g of methyl isobutyl ketone are added.

EXAMPLE 2 600 g of this resin are then mixed with 750 g of preproduct 1V and heated to 110C until the viscosity, measured at 50 7( strength in ethyl isobutyl ketone at 25C, has risen to 300 cP. The solvent is removed by vacuum distillation and the resin is diluted to a solids content of 75 with ethylene glycol monobutyl ether. After neutralisation with ammonia, the resin can be diluted with water in all proportions.

The resin can be used as an electrophoretic singlecoat resin and after stoving for 30 minutes at 170C gives films of very good resistance to wash lyes.

MANUFACTURE OF COMPONENT a 400 g of Z-ethylhexyl acrylate,

150 g of allyloxypropanol,

250 g of styrene.

g of acrylic acid,

20 g'of laurylmercaptan and 30 g of di-tert.-butylperoxide are mixed. 250 g of the mixture are heated to 130C under reflux in a nitrogen gas atmosphere. After 40 minutes the remaining portion (three-fourths of the above mixture) are added dropwise and the mix is kept at 130C until the solid content amounts to 96 7( by weight. the monomers not reacted are removed by vac uum distillation, and the resin component a is diluted with 200 g of methyl isobutyl ketone.

MANUFACTURE OF COMPONENT a 200 g of butylene glycol and 400 g of vinylversatate are mixed. To this mixutre, which is kept in a flask with reflux condenser through which nitrogen gas is passed, a mixture of 200 g of acrylic acid,

200 g of hydroxyethyl acrylate,

200 g of methylmethacrylate,

g of di-tert.-butylperoxide,

10 g of laurylmercaptan and 200 g of butylene glycol is added dropwise.

After all is added, the reaction is continued by keeping the mix at 130C until the solid content amounts to 70 by weight. The solvent is removed vy vacuum distillation, and the resin component (/1 is diluted with 250 g of methylisobutyl ketone.

MANUFACTURE OF COMPONENT a The procedure is as in the manufactue of component a however, a mixture of 490 g of vinylversatate and 200 g of butylene glycol is employed as the starting mixture. A mixture of 200 g of acrylic acid,

160 g of hydroxybutyl acrylate,

150 g of methylmethacrylate,

25 g of.di-tert.-butylperoxide,

10 g of laurylmercaptan and 200 g of ethylene glycol monobutyl ether is added dropwise. The resin component a is also diluted with 250 g of methylisobutyl ketone after the solvent has been distilled off.

MANUFACTURE OF COMPONENT a 1 The procedure is as in the manufacture of component (1 however, a mixture of 500 g of vinylversatate and 200 g of ethylene glycol monobutyl ether is employed-as the mixture. v

A mixture of 200 g of acrylic acid,

150 g of hydroxymethyl methacrylate.

25 g of di-tert.-butylperoxide,

5 g of laurylmercaptan and 200 g of ethylene glycol monobutyl ether is added dropwise. The resin component-a is diluted with 300 g of methyl ethyl ketone after removal of solvents by vacuum distillation.

MANUFACTURE OF COMPONENT a,

A mixture of v I 200 g of acrylic acid, 1 l

150 g of hydroxymethyl methacrylate.

400 g of Z-ethylhexyl acrylate,

250 g of styrene,

30 g of di-tert.-butylperoxide and 15 g of laurylinercaptan are added dropwise at 130C to 400 g of ethylene glycol monobutyl ether in a flask equipped with reflux condenser through which nitrogen gas is passed. The reaction is carried on at 130C until the solids content amounts to by weight. The the solvent is removed by vacuum distillation and the resin component a is diluted with 350 g of ethyl acetate.

MANUFACTURE OF COMPONENT a A mixture of 200 g ofacrylic acid,

150 g of hydroxyethyl methacrylate,

400 g of 2-ethylhexyl acrylate,

250 g of acrylonitrile,

20 g of di-tert.-butylperoxide and 25 g of laurylmercaptan is added dropwise to 400 g of xylene contained in a flask with reflux condenser through which nitrogen gas is passed, at reflux temperature. The reaction is continued at 130C until a solids content of 70 by weight is reached. A solution of component a in xylene is obtained.

EXAMPLE 3 The'resin solution a is mixed with pre-product 11 in the weight ration 6:4 (relative to solids content). The mixture is heated to to C until the viscosity amounts to'500 cP, measured as 50 70 strength solution in methyl isobutyl ketone at 25C. Then the solvent is removed by vacuum distillation and thereaction product is diluted to a solics content of 70 70 by weight using ethylene glycol m'onoethyl ether. After neutralising the obtained reaction product with dimethyl ethanol amine the product can be diluted with water in all proportions.

This" solutionis especially suited for electrophoretic prime r'coating and is furthermore suited for coatings, which are stable to wash lyes, in those cases in which a stronger yellowing during stoving of the resin is of no importance. The stoving of the coatings takes place at C in 20 to 30 minutes.

13 EXAMPLE 4 The resin solution 21 is mixed with pre-product 111 in the weight ration of 1:3 (relative to solids content).

The mix is heated to l C until the viscosity amounts to 320 cP at 25C measured as 50 strength solution in methyl isobutyl ketone. The solvent is removed by vacuum distillation, and the obtained reaction product is diluted with ethylene glycol monoethyl ether to a solids content of 70 7: by weight. After addition of such quantity of ammonia until a pH-value of 7.5 is reached. the neutralised product can be applied as single-coat binder. The thus produced films can be stoved at 170 in 30 minutes. p I

EXAMPLE 5 The resin solution a is mixed with pre-product V in the weight ration of 6:4 (relative to the solidscontent). The mixture is heated to 970C and kept at this temperature until the viscosity rose to 270 cP, measured at 25C as 50 strength solution in methyl isobutyl ketone. The solvent is removed by vacuum distillation and the obtained reaction product is diluted with ethylene glycol monobutyl ether to a solids content of 70 7r by weight. The reaction product is in all "proportions waterdilutable after neutralisation with diisopropanol amine. The product is very suitable for the manufacture of single-layer coatings being deposited electrophoretically and stoved at 170C in to 30 minutes. These coatings are weather-resistant and stable to wash lye.

EXAMPLE 6 The resin solution a is mixed with pre-product V1 in the weight ration,6:4 (relative tosolid content). The mix is heated to 90lOOC and kept at this temperature until the viscosity rose to 480 cP, measured at 50 70 strength solution in methyl isobutyl ketone at C. The solvent is then removed by vacuum distillation. The obtained reaction product vis,di1uted to a solids content of 70 by weight using ethylene glycol monobutyl ether. After being neutralised with triethyl amine, the reaction product can be diluted with .water in all proportions. The product is suitable as single-coat lac quer which is applied electrophoretically and stoved at 170C for minutes. The coatings show a good stability to wash lye.

EXAMPLE 7 The resin solution a is mixed'withpre-product VII in the weight ratio of 5.5:4.5 (relative to solids content). The mix is heated to 100C and kept at this temperature until the viscosity amounts to 500 cP at 25C measured at 50 strength solution in methyl isobutyl ketone. The solvent is removed by vacuum distillation, and the obtained reaction product'is diluted to a solids content of 70 by weight using a mixture ofequal parts of ethylene glycol monobutyl ether and sec. butanol. After neutralisation with diisopropanol amine the product is dilutable with water in all proportions. The product may be used for the manufacture of highly glossy single-layer coatings deposited electrophoretically which show very good stability to wash lye after 30 minutes stoving time at 170C.

EXAMPLE 8 The resin solution a is mixed with pre-product Vlll {content of 70 7c by weight using ethylene glycol monobutyl ether. After neutralisation with dimethyl ethanol amide the product may be used as binder for singlecoat lacquers. Films made thereof are stoved at 170C for 30 minutes and are stable to wash lye.

EXAMPLE 9 The resin solution a is mixed with pre-product Vlll in the weight ration of l: l (relative to solids content). The mix is heated .to 100C and is kept at this tempera- ,ture until the viscosity amounts to 270 cP at 25C measured as 50 V1 strength solution in methyl isobutyl ketone. Then the solvent is removed by vacuum distillation. The obtained reaction product is diluted to a solids content-of 7: by weightusing a mixture of equal parts ethylene glycol monobutyl ether and ethylene glycol monoethyl ether. After neutralising with ammonia the product may'be used as binder for themanufactureof single-coat lacquers. Films thus obtained can be stoved at C for 30 minutes and show the follow ing properties: good stability to wash lye and-good resrstance against corrosion.

INVESTIGATIONS TO DEMONSTRATE THE TECHNICAL ADVANCE ACHIEVED l. A resin according to Example 1 of the present invention was manufactured.

2. A resin according to Example 1 of French Patent Specification 1,524,720 was manufactured. 3. Aresin according to Example 11 of German fenlegungsschrift 2,020,905 was manufactured.

4.,A resin according to Example 1 of German Offenlegungsschrift 2,118,692 or US. Pat. No. 3,773,729 was manufactured. The resin, in the solution described, displayed a strong thixotropy. h

5. 330 partsof the product described as partially blockedisocyanate -1 in German Offenlegungsschrift 2,118,692 or U.S..Pat. No. 3,773,729 were added dropwise at 80C- to 1,150 parts of the acrylic resin described in Example 1 of the present invention. After a reaction time of 1 hour,=the batch gelled. The resins according to No. l4 were pigmented with titanium dioxide using a pigment/binder ratio of 0.3:1. Resins No. l, 2 and 4.were then neutralised with triethylamine and the pigment pastes were diluted to a solids content of 12 with deionised water. Zincphosphatised sheets were coated electrophoreticallyin these baths, to produce a coating thickness of about 22-25 a, and the coating was stoved for 30 minutes at 1 80C. The. resin according to No. 3 was diluted to spraying viscosity with water and a zinc-phosphatised sheet was also coated to a coating thickness of 22-25 p. by spraying and the coating stoved for 30 minutes at C. The salt spray resistance (ASTM-B-1l4-64) and the wash lye resistance (treatment with 2 strength detergent solution for 8 hours at the boil and 8 hours cold=1 cycle) were tested.

No. l No. 2 No. 3 No. 4

ASTM

120 hours (best value I. l 3 5 3 worst value 5) Wash lye resistance 2 cycles. 0.5 cycle. 0.2 cycle. 0.8 cycle.

in order completely completely completely destroyed destroyed destroyed By parts parts by weight are meant. What is claimed is: 2. Process according to claim I wherein component 1. Process for the manufacture of thermosetting synthetic resins with urethane groups, which contain carboxyl groups and masked isocyanate groups and can be diluted with water after neutralization with ammonia or amines. and which are manufactured by reaction of a compound (a) which contains alcoholic hydroxyl groups and carboxyl groups, with a masked isocyanate (b) in inert organic solvents, characterized in that as the compound (a) there are used copolymers of two or more vinyl monomers. individually or as mixtures thereof. which contain alcoholic hydroxyl groups and carboxyl groups, have a molecular weight of about 300 to 10.000, a hydroxyl equivalent weight of 200 to 900 and'acid numbers of about 30 to 150. based on carboxyl groups, and which must be soluble in inert polar organic solvents, only those copolymers being employed of which the carboxyl groups are not capable of significant reaction with masked isocyanate groups at temperatures of 80 to I50C over the course of about one hour, and as the masked isocyanate (b) there is used a polyurethane which contains at least one masked isocyanate group and which has been obtained by reaction of a polyisocyanate with a free isocyanate group and at least one masked isocyanate and at most up to masked isocyanate groups with a compound carrying alcoholic hydroxyl groups, having a molecular weight of about l2,000 and a hydroxyl equivalent weight of about 60-500, the compound having been chosen from the group consisting of esters of fatty acids with polyols. wherein the polyols should be at least trifun ctional. and diols which carry terminal hydroxyl groups and in which 3 to 8 carbon atoms are aliphatically bonded between the hydroxyl groups. and that the components (a) plus (h) are reacted at temperatures of 80-l 50C, that the component (a) is employed in such amounts that the end product has acid numbers between about and l20. that thee proportion of calculated isocyanate groups introduced when manufacturing the component (b) is between 7.5 and 20 percent by weight relative to the weight of the end product and (0) comprises copolymers of 420 percent of acrylic acid. methacrylic acid or mixtures of acrylic acid and methacrylic acid. 40-70 percent of plasticizing copolymerized monomers selected from the group consisting of alkyl acrylates or alkyl methacrylates in which the alkyl radical contains 4 to 12 carbon atoms. and optionally 5-35 percent of styrene. vinyltoulene or acrylonitrile, 8 to 15 percent of hydroxyalkyl acrylate being contained in the acrylate or methacrylate copolymer. said hydroxyalkyl acrylate or methacrylate being defined by the general formula: 5

wherein n represents values between 2 and 6. R is hydrogen or a methyl group and the compound of the formula (l) or mixtures of these compounds have hydroxy numbers of about to 200.

3. Process according to claim 2 wherein the plasticizing copolymerized monomers includes an allyl compound selected from the group consisting of allyl alcohol. allyloxy propanol, trimethyl propane diallyl ether, pentaerythritol triallyl ether in place of the hydroxyalkyl acrylate or methacrylate component.

4. Process according to claim 2 wherein the plasticizing monomer is a vinyl ester of an a-alkylalkane monocarboxylic acid which is a mixture of C C and C monocarboxylic acids.

5. Process according to claim 1 wherein the masked polyisocyanates are mixtures of 65-80 percent by weight of 2.4-toluylene diisocyanate or hexamethylene diisocyanate and 35-20 percent by weight of 2,6- toluylene diisocyanate or hexamethylene diisocyanate.

6. Process according to claim 1 wherein the masked polyisocyanates employed contain phenol or e-caprolactam as masking component.

7. A thermosetting synthetic resin produced according to the process of claim 1.

8. A process according to claim 1 wherein the esters of the fatty acids are with polyols which contain more than 3 but at most 6 hydroxyl groups per molecule.

CH CH:l

UNITED STATES PATENT OFFICE CERTIFICATE OF CDRRECTXUN 9 Patent No. 3,897,377 1 Dated July 29, 1975 n org) Bernhard Broe cker and Wolfram Plettner It is certified that error appears in the abofie-identified patent Q and that said Letters Patent are hereby corrected as shown below:

[73] 'Assignee: -HOECHST AKTIENGESELLSCHAFT', Frankfurt, Germany-- Col:. 6,. li ne 42: "at" -as-- cc1.- 8,. line 24; f'possble! possible- Col. 11,.Tline 50: "vy" --by Col. 12, line 57: "solics" v -solids 001.13, line 3: "1:3" -7=3'---- Col. 15, lihe lO: "By zparts;parts -By parts, part c 1.15, line 418.: "thee" ----the-- 1 I Signed and Sealed this twenty-fourth Day Of February 1976 [SEAL] Arrest.

' RUTH C. MASON c. MARSHALL DANN Atltsling ()ffl'te Commissioner uj'lalenls and Trademarks 

2. Process according to claim 1 wherein component (a) comprises copolymers of 4-20 percent of acrylic acid, methacrylic acid or mixtures of acrylic acid and methacrylic acid, 40-70 percent of plasticizing copolymerized monomers selected from the group consisting of alkyl acrylates or alkyl methacrylates in which the alkyl radical contains 4 to 12 carbon atoms, and optionally 5-35 percent of styrene, vinyltoulene or acrylonitrile, 8 to 15 percent of hydroxyalkyl acrylate being contained in the acrylate or methacrylate copolymer, said hydroxyalkyl acrylate or methacrylate being defined by the general formula:
 3. Process according to claim 2 wherein the plasticizing copolymerized monomers includes an allyl compound selected from the group consisting of allyl alcohol, allyloxy propanol, trimethyl propane diallyl ether, pentaerythritol triallyl ether in place of the hydroxyalkyl acrylate or methacrylate component.
 4. Process according to claim 2 wherein the plasticizing monomer is a vinyl ester of an Alpha -alkylalkane monocarboxylic acid which is a mixture of C9-, C10- and C11- monocarboxylic acids.
 5. Process according to claim 1 wherein the masked polyisocyanates are mixtures of 65-80 percent by weight of 2,4-toluylene diisocyanate or hexamethylene diisocyanate and 35-20 percent by weight of 2,6-toluylene diisocyanate or hexamethylene diisocyanate.
 6. Process according to claim 1 wherein the masked polyisocyanates employed contain phenol or epsilon -caprolactam as masking component.
 7. A thermosetting synthetic resin produced according to the process of claim
 1. 8. A process according to claim 1 wherein the esters of the fatty acids are with polyols which contain more than 3 but at most 6 hydroxyl groups per molecule. 